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We investigate the performance of Pd films on siloxane underlayer for the development of H2 sensors based on the surface plasmon resonance (SPR) effect. Reflectance measurements were carried out on sputtered Pd films on bare glass and on glass pre-coated with a siloxane layer, using Kretschmann's prism coupling configuration. For most of the range of Pd thicknesses investigated, the sensitivity for H2 detection on bare glass was higher than that on Pd-siloxane, with the maximum sensitivity for the latter matching that on bare Pd. A direct comparison between the sensitivity data for the two multilayer configurations, indicates a trend of improved sensitivity for H2 at higher thickness values for the siloxinated palladium films.